JPH10177265A - Production of light accepting member, light accepting member by that method, electrophotographic device having the member and electrophotographic process using the member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent cleaning property and to prevent splashing of a toner and contamination of wires by alternately repeating film forming processes and etching processes for plural times to form a surface layer comprising a noncrystalline material containing at least boron atoms and nitrogen atoms in a reaction chamber which can be evacuated. SOLUTION: After an amorphous boron nitride (a-BN) is formed in a reaction chamber which can be evacuated, a fluorine-based gas is introduced to etch the surface of the layer to form a region 102 containing fluorine atoms in a bonded state. Then an a-BN thin film is again deposited to form a region 101 where fluorine atoms are diffused by the surface reaction. Then the surface is etched with a fluorine-based gas same as above described. By repeating these processes to obtain desired thickness, plural regions 101 having diffusion of fluorine atoms can be formed, and thereby, a surface layer having high hardness and high water repelling property can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a light receiving member, a light receiving member manufactured by the method, an electrophotographic apparatus having the light receiving member, and an electrophotographic process using the light receiving member. In more detail, it is excellent in cleaning property, without providing a heating means for the light receiving member,
A method for manufacturing a light-receiving member, a light-receiving member manufactured by the method, an electrophotographic apparatus having the light-receiving member, and a method for obtaining a high-quality image free of image blur and image deletion under any environment. And an electrophotographic process using the light receiving member.

[0002]

2. Description of the Related Art Various materials such as inorganic materials such as selenium, cadmium sulfide, zinc oxide, amorphous silicon (hereinafter referred to as a-Si), and organic materials are used as materials for a light receiving member used in an electrophotographic photosensitive member. Has been proposed. Among these, non-single crystalline deposited films containing silicon atoms typified by a-Si as a main component, for example, include hydrogen and / or halogen (for example, fluorine, chlorine, etc.) (for example, compensate for hydrogen or dangling bonds) ) A-S
Amorphous deposited films such as i have been proposed as high-performance, high-durability, pollution-free photoconductors, and some of them have been put to practical use. JP-A-54-86341, USP 4,26
No. 5,991 discloses a technique of an electrophotographic photosensitive member in which a photoconductive layer is mainly formed of a-Si.

An a-Si based photoreceptor represented by a-Si has a high surface hardness and a semiconductor laser (770 to 800 nm).
m) It has high sensitivity to long-wavelength light, such as m), and has excellent features such as almost no deterioration due to repeated use. Therefore, it is suitable for electrophotographic photoreceptors such as high-speed copying machines and LBPs (laser beam printers). Widely used.

As a method of forming a silicon-based non-single-crystal deposited film, there are a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (photo CVD method), and a method of decomposing a source gas by plasma. Many methods are known, such as a method of decomposing gas (plasma CVD method). Among them, the plasma CVD method, that is, the raw material gas is decomposed by direct current or high frequency, (RF, VHF) or glow discharge generated by using microwave, glass, quartz, heat-resistant synthetic resin film, stainless steel, aluminum, etc. The method of forming a deposited film on a desired substrate of
Not only the method of forming an amorphous silicon deposited film for electrophotography, but also the method of forming a deposited film for other uses is currently in very practical use, and various apparatuses have been proposed for that purpose.

Further, in view of application to electrophotographic photoreceptors, in recent years, there has been a strong demand for improvements in film quality and processing ability, and various devices have been studied. In particular, a plasma process using high-frequency power is used because of its various advantages, such as high discharge stability and the ability to be used for forming insulating materials such as oxide films and nitride films.

Recently, a parallel plate type plasma CV has been developed.
There is a report on a plasma CVD method using a high frequency power supply of 20 MHz or more using a D apparatus (Plasms Chemistry and P
lasms Processing, Vol.7, No.3 (1987) p267-273), Possibility of improving deposition rate without lowering the performance of deposited film by increasing discharge frequency from conventional 13.56 MHz Is shown and attracted attention. In addition, reports of increasing the discharge frequency are also made by sputtering or the like,
In recent years, it has been widely studied.

[0007]

By the way, in most cases, a wire electrode (for example, 50 to 50) is used as a means for charging and discharging various conventional light receiving members including an a-Si light receiving member.
Corona chargers (corotrons, scorotrons) mainly using a 100 μmφ gold-plated metal wire such as a tungsten wire and a shield plate are used. That is, a high voltage (4 to 8 k) is applied to the wire electrode of the corona charger.
(Approximately V) is applied to the surface of the photoreceptor member to cause the corona current to be applied to the surface of the photoreceptor member to perform charging and static elimination. The corona charger is excellent in uniform charging and static elimination.

However, a considerable amount of ozone (O ₃ ) is generated due to the corona discharge. The generated ozone oxidizes nitrogen in the air to produce nitrogen oxides (NO _x ) and the like. Furthermore, the produced nitrogen oxides and the like react with moisture in the air to generate nitric acid and the like. Corona discharge products such as nitrogen oxides and nitric acid adhere to and accumulate on the photoreceptor and peripheral devices, and contaminate the surfaces thereof.

Such a corona discharge product has a strong hygroscopic property, and the surface of the light-receiving member to which the corona discharge product is adsorbed has a low resistance due to the moisture absorption of the adhered corona discharge product. Partial decrease in image quality, image blurring or image deletion (state in which the surface charge of the photoreceptor leaks in the surface direction and the electrostatic latent image pattern collapses or is not formed)
In some cases, this may cause an image defect referred to as an image defect.

Further, the corona discharge products adhered to the inner surface of the shield plate of the corona charger are volatilized and released not only during the operation of the electrophotographic apparatus, but also during the stoppage of the apparatus at night or the like. The volatilized and released corona discharge product adheres to the surface of the light receiving member corresponding to the discharge opening of the charger and further absorbs moisture. Therefore, the surface of the light receiving member may be reduced in resistance. For this reason, the first sheet output at the time of restarting the apparatus after the apparatus is stopped, or several subsequent copies, is provided with image blur and image flow in an area corresponding to the charger opening when the apparatus is stopped. Easy to occur. This is particularly likely to occur when the corona charger is an AC corona charger. Further, when the light receiving member is an a-Si light receiving member, the problem of image blur and image deletion due to the above-described corona discharge product may increase.

That is, the a-Si-based light receiving member has a lower charging and discharging efficiency than the other light receiving members (the corona charging current required for obtaining a desired charging and discharging potential is large), For this reason, in the charging and discharging of the a-Si-based light receiving member by corona discharge, the voltage applied to the charger is made higher than in the case of other light receiving members to greatly increase the amount of charging current. . The a-Si light receiving member is often used particularly in a high-speed electrophotographic apparatus. In such a case, the charging current amount is, for example, 2,000.
may reach μA.

Since the corona charging current amount and the ozone generation amount are in a proportional relationship, when the light receiving member is an a-Si based light receiving member, and the light receiving member is charged and destaticized by corona charging, it is particularly required. The amount of ozone generated is increased, and therefore, the problem of image blur and image deletion due to the generation of the corona discharge product may be particularly large.

Further, in the case of the a-Si light receiving member, since the surface hardness is extremely high as compared with other photoreceptors, it is difficult to remove attached matter together with the light receiving member in a cleaning step or the like. The corona discharge product attached to the
It tends to remain forever.

Therefore, conventionally, a heater for heating the light receiving member is built in the light receiving member, or warm air is blown to the light receiving member by a hot air blower to heat the surface of the light receiving member. (30 to 50 ° C.) to keep it in a dry state, thereby preventing the corona discharge product adhering to the surface of the light receiving member from absorbing moisture and substantially reducing the resistance of the surface of the light receiving member. Measures may be taken to prevent blurring and image deletion. Particularly in the case of an a-Si light receiving member,
This heating and drying means is incorporated in an electrophotographic apparatus as an indispensable one.

The developing device of such an electrophotographic apparatus is provided with a rotating cylindrical developer carrier having, for example, a movable magnet or the like, and a developer, that is, a toner and a mixture of a toner and a carrier, are provided on the carrier. After the thin layers are formed, a method of electrostatically transferring these onto a light receiving member on which an electrostatic latent image is formed is widely used. JP-A-54-4
3037, 58-144865 and 60-7451 disclose examples of these systems. As the developer, a developer containing magnetic particles, that is, a mixture of a toner and a carrier, or a developer containing magnetite or the like in a toner and containing no carrier can be used.

In such a system, since the light receiving member-facing portion of the rotary cylindrical developer carrier expands due to the heat of the light receiving member while the apparatus is at rest, the rotating cylindrical developer carrier in the developer developing section is expanded. The distance between the body and the light receiving member may be reduced. For this reason, the electric field in the meantime becomes strong and the developer is more easily transferred than usual. In addition, the portion on the opposite side of the portion has a longer distance due to the influence, and thus the electric field becomes smaller, so that the developer may be harder to transfer than usual. As a result, the image density may partially increase or decrease in the rotation cycle of the rotating cylindrical developer carrier, and the development of such development significantly impairs the quality of the output image of the electrophotographic apparatus. There was a case. Therefore, there has been a demand for a light receiving member that does not cause image blur or image deletion without heating the light receiving member.

Further, charging, exposure, development, transfer, separation,
In an electrophotographic apparatus in which each step of cleaning is sequentially repeated to perform scrape cleaning with a blade, the frictional resistance of the light receiving member may gradually increase due to repeated operations. When the frictional resistance increases, the cleaning performance of the residual developer (toner) is significantly reduced.

When the copying process is repeated in such a state, the fine particles of the developer and the external additives (such as strontium titanate and silica) contained in the developer are scattered in the corona charger and the corona charger is charged with fine particles. It may adhere to a wire electrode (hereinafter, referred to as a charger wire) and cause uneven discharge. If discharge unevenness occurs due to contamination of the charger wire, in normal development (a method of developing a non-exposed portion on the surface of the light receiving member), a streak-like white spot on an image, a scale-like black haze spreading over the entire image, and a period. In some cases, black spots (0.1 to 0.3 mmφ) or the like which are locally generated without causing the image quality may be reduced. In addition, when the charger wire stains occur, abnormal discharge is induced between the stained portion and the light receiving member, and the surface of the light receiving member may be destroyed to cause an image defect.

The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide an electronic apparatus for performing scrape cleaning with a blade by repeating charging, exposure, development, transfer, separation, and cleaning steps sequentially. A photoreceptor which has a low frictional resistance in a photographic device, prevents toner from scattering, and does not cause contamination of a charger wire, and has no or substantially no adhesion of corona discharge products generated by corona discharge. A light receiving member that provides a receiving member and can obtain a high-quality image free from image blur and image deletion without providing a heating unit for the light receiving member regardless of environmental conditions, and an electrophotograph having the light receiving member. It is an object of the present invention to provide an apparatus and a method for manufacturing the light receiving member.

The present invention also provides a reaction vessel capable of reducing pressure,
A method of manufacturing a light receiving member for forming the surface layer by alternately repeating the film formation and etching of a layer of a non-single crystal material containing boron atoms and nitrogen atoms on a substrate a plurality of times. An object of the present invention is to provide a light receiving member, and an electrophotographic apparatus and an electrophotographic process having the light receiving member.

[0021]

According to the present invention, a non-single crystal material containing at least boron atoms and nitrogen atoms is formed by alternately repeating film formation and etching a plurality of times in a reaction vessel capable of reducing pressure. The present invention provides a method for producing a light receiving member having a coated surface layer, a light receiving member produced by the method, an electrophotographic apparatus having the light receiving member, and an electrophotographic process using the light receiving member. .

In the present invention, it is preferable that film formation and / or etching is performed using high-frequency power having a discharge frequency of 50 to 450 MHz. Further, the surface layer may further contain hydrogen.

In the present invention, it is preferable that a fluorine atom be contained in the entire surface layer in the thickness direction.

Further, it is desirable to use a fluorine-based gas as a gas used for etching, and to make the thickness to be etched preferably 20 Å or more, more preferably 50 Å or more.
When the fluorine-based gas is CF ₄ or CHF ₃ or C ₂ F ₆
Or it is desirable to be ClF ₃ .

The thickness of the surface layer formed by one film formation and etching is preferably 10 to 2,000 angstroms, more preferably 40 to 1,000 angstroms.

The surface layer may be provided on the light receiving member, and the receiving layer may have photoconductivity or may have a photoconductive layer. The photoconductive layer may be of a single-layer type, or the photoconductive layer may be of a function-separated type.

In the present invention, by adding fluorine atoms to the surface layer by the above method, the water repellency of the surface layer can be improved, and the adhesion of corona discharge products can be effectively prevented.

The present inventor has considered that a boron atom, a nitrogen atom,
With respect to a surface layer containing hydrogen atoms, unbonded boron atoms and nitrogen atoms or BH bonds and NH bonds present in the film of the surface layer are converted to BF bonds and NF bonds. As a result of studying high water repellency, it was found that a durable and extremely high water repellent surface layer was obtained. This comparison of water repellency is an evaluation based on the contact angle when a drop of pure water is placed on the evaluation sample. It is evaluated that the larger the contact angle, the higher the water repellency.

On the other hand, for example, Japanese Patent Application Laid-Open No. 61-289354
In the case of fluorinating only the outermost surface of the surface layer as disclosed in, an electrophotographic apparatus that performs each step of charging, exposure, development, transfer, separation, and cleaning sequentially and performs scrape cleaning with a blade, It has been found that since the outermost surface of the light receiving layer is polished by the toner and the abrasive contained in the toner, the effect of water repellency becomes insufficient due to repeated operations. Also, an attempt was made to positively incorporate fluorine atoms into the surface layer using a fluorine-based gas.However, when a plasma processing apparatus using high-frequency power is used, it is not possible to include fluorine atoms in a film as desired. Not easy. Even if a desired amount of fluorine atoms can be contained in the film, there is a point that further improvement is desired, such as a long time required for deposition.

As a result of various studies on the above problem, the present inventor has found that as a method of including fluorine atoms in the surface layer, the surface to be deposited is coated with fluorine atoms in advance, so that the fluorine atoms are deposited on the surface of the deposited film during film formation. And a boron atom and a nitrogen atom interact with each other, and the boron atom and the nitrogen atom form a three-dimensional network, and the fluorine atom is incorporated as a terminator.
As a result, fluorine atoms can be contained while providing sufficient mechanical strength as a surface layer of the electrophotographic light-receiving member, and at the same time, high water repellency can be provided. In addition, in the case of this method, the deposition rate was the same as that in the case where the surface was not coated with fluorine atoms, and it was possible to form a film at a deposition rate sufficient for practical use.

Further, even if a fluorine-based gas is used as the film forming gas for the surface layer, the use of high-frequency power having a frequency of 50 to 450 MHz allows efficient deposition of the film without impairing the deposition rate and mechanical strength. Was found that a fluorine atom was incorporated into.

Further, in an electrophotographic apparatus in which charging, exposure, development, transfer, separation, and cleaning steps are sequentially repeated to perform scrape cleaning with a blade, the outermost surface of the light receiving layer is exposed to the toner and an abrasive contained in the toner. Even if polished, it is possible to always maintain a fluorine-containing high water-repellent surface while maintaining the hardness as a surface protective layer and the initial frictional resistance. For this reason, they have found that they have excellent cleaning properties, do not cause toner scattering, and have an effect of preventing wire contamination.

[0033]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. In FIG. 1, the surface layer has a four-layer structure, but the surface layer may have any number of layers as long as it has a plurality of layers, but is generally preferably in the range of 2 to 50 layers. With respect to the outermost surface, it is particularly preferable that the film has been subjected to an etching treatment. The thickness of the film deposited in one film formation can be appropriately determined as desired, but is preferably from 30 to 2
500 angstroms, more preferably 60-100
0 angstrom. Further, the film forming conditions of each layer may be constant for all layers or may be changed. For example, the film may be formed such that the fluorine content increases toward the surface.

As a method of containing fluorine atoms in the entire surface layer, a thin layer of amorphous boron nitride (hereinafter referred to as a-BN) is deposited to form a normal light-receiving layer, and then a fluorine-based layer is formed. By introducing a gas and etching the surface, fluorine atoms are bonded to the surface. Next, a thin film of a-BN is deposited thereon again,
An a-BN film containing fluorine is formed by utilizing a surface reaction. The surface is etched with a fluorine-based gas in the same manner as described above, and this operation is repeated until a desired thickness is obtained, whereby a region containing a plurality of fluorine atoms can be formed, thereby providing a high hardness and high hardness. A water-repellent surface layer can be obtained.

The thickness of the layer removed by etching also has a relationship with the thickness of the formed layer.
2000 angstroms, more preferably 50-50
0 Å is preferred.

The thickness of the region where the fluorine atoms are bonded is preferably 1 to 500 angstroms, more preferably 10 to 50 angstroms. CF ₄ , CHF ₃ , CH
₂ F _2, CH ₃ F, a fluorine-based gas such as C ₂ F _6, ClF ₃ is preferably used.

FIG. 2 is a diagram schematically showing an example of an apparatus for depositing a light receiving member by a plasma CVD method using a high-frequency power supply according to the present invention. This apparatus is roughly classified into a deposition apparatus 2100, a source gas supply apparatus 2200, and a reaction vessel 21.
The apparatus 10 includes an exhaust device (not shown) for reducing the pressure inside the apparatus 10. A cylindrical deposition substrate 2112 connected to the ground, a heater 2113 for heating the cylindrical deposition substrate, and a source gas introduction pipe 2114 are installed in a reaction vessel 2110 in the deposition apparatus 2100. The high frequency power supply 2120 is connected via the.

The raw material gas supply device 2200 includes SiH ₄ ,
Source gas cylinders such as H ₂ , CH ₄ , NO, B ₂ H ₆ , CF _{4 and the} like, and etching gas cylinders 2221-2226 and valves 2231-2236, 2241-2246, 22
51 to 2256 and mass flow controller 221
Each of the constituent gas cylinders is connected to a gas introduction pipe 2 in the reaction vessel 2110 via a valve 2260.
114 is connected.

As the high-frequency power supply used for forming the surface layer of the present invention, a power supply having a frequency in the range of 50 to 450 MHz can be suitably used. At a discharge frequency of 450 MHz or higher, the stability and uniformity of the discharge are not sufficient, and the discharge is locally concentrated. As a result, the thickness of the deposited film may be uneven. The output is 10
Although the range of 5000 W is preferable, the range of output is not limited as long as power suitable for the device to be used can be generated. Further, the output fluctuation rate of the high-frequency power supply is not limited as long as a desired film can be formed.

The cylindrical film-forming substrate 2112 is connected to the ground by being placed on the conductive support 2123. Further, the cathode electrode 2111 is made of a conductive material and is insulated by the insulating material 2121. As a conductive material used for the conductive cradle 2123, copper, aluminum, gold, silver, platinum, lead, nickel, cobalt,
Iron, chromium, molybdenum, titanium, stainless steel and
Two or more composite materials of these materials can be used.

As an insulating material for insulating the cathode electrode 2111, an insulating material such as ceramics, Teflon, mica, glass, quartz, silicone rubber, polyethylene and polypropylene can be used.

As the matching box 2115, any structure can be suitably used as long as it can match the load with the high frequency power supply 2120. Further, as a method for obtaining the matching, it is preferable that the adjustment is performed automatically. However, even if the adjustment is performed manually, the effect of the present invention is not affected at all.

Cathode electrode 21 to which high-frequency power is applied
Examples of the material 11 include copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and composite materials of two or more of these materials. The shape is preferably a cylindrical shape, but an elliptical shape or a polygonal shape may be used if necessary.

The cathode electrode 2111 may be provided with a cooling means if necessary. As a specific cooling means, cooling with water, air, liquid nitrogen, a Peltier element or the like is used as necessary. In FIG. 2, the reaction vessel 2110
An example is shown in which an insulating shield plate is provided around the periphery.

The cylindrical film-forming substrate 2112 used in the present invention
May have any material or shape according to the purpose of use. For example, the shape is preferably cylindrical when an electrophotographic photoreceptor is manufactured, but may be flat or another shape if necessary. In addition, in the material, copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and a composite material of two or more of these materials,
Furthermore, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass,
An insulating material such as quartz, ceramics, paper or the like coated with a conductive material can be used.

An example of a procedure of a method for forming a light receiving member using the apparatus shown in FIG. 2 will be described below. Reaction vessel 21
10, a cylindrical film-forming substrate 2112 is installed, and a reaction vessel 2110 is formed by an exhaust device (not shown) (for example, a vacuum pump).
Exhaust the inside. Subsequently, the temperature of the cylindrical film-forming substrate 2112 is set to 20 by the heater 2113 for heating the film-forming substrate.
Control to the desired temperature of ~ 500 ° C. Next, it is confirmed that the valves 2231 to 2236 of the gas cylinder and the leak valve 2117 of the reaction container are closed to allow the source gas for forming the light receiving member to flow into the reaction container 2110. After confirming that 2246, the outflow valves 2251 to 2256, and the auxiliary valve 2260 are open, the main valve 2118 is opened to exhaust the reaction vessel 2110 and the gas supply pipe 2116.

Thereafter, the reading of the vacuum system 2119 is 5 × 10
^{When the} pressure reaches ^-6 Torr, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed. Then gas cylinder 2
From 221 to 2226, each gas is supplied to a valve 2231 to 223.
6 is opened and introduced, and each gas pressure is adjusted to ² kg / cm ² by the pressure adjusters 2261 to 2266. Next, the inflow valves 2241 to 2246 are gradually opened to introduce each gas into the mass flow controllers 2211 to 2216.

After the preparation for film formation is completed by the above procedure, a photoconductive layer is first formed on the cylindrical substrate 2112 for film formation. That is, when the cylindrical film-forming substrate 2112 reaches a desired temperature, each of the outflow valves 2251 to 2225
56 and the auxiliary valve 2260 are gradually opened, and a desired raw material gas is supplied from each of the gas cylinders 2221 to 2226 through the gas introduction pipe 2114 to the reaction vessel 2110.
Introduce within. Next, each mass flow controller 221
According to 1-2216, each source gas is adjusted so as to have a desired flow rate. At this time, the inside of the reaction vessel 2110 is 1 To
The opening of the main valve 2118 is adjusted while watching the vacuum gauge 2119 so that the desired pressure is equal to or lower than rr. When the internal pressure is stabilized, the high-frequency power supply 2120 is set to a desired power, and for example, high-frequency power of a frequency of 1 to 450 MHz is supplied to the cathode electrode 2111 through the high-frequency matching box 2115 to generate a high-frequency glow discharge. The respective source gases introduced into the reaction vessel 2110 are decomposed by the discharge energy, and the cylindrical substrate 2 is formed.
A photoconductive layer mainly composed of desired silicon atoms is deposited on 112. After the formation of the desired film thickness, the supply of the high-frequency power is stopped, the outflow valves 2251 to 2256 are closed, and the inflow of each source gas into the reaction vessel 2110 is stopped.
The formation of the photoconductive layer is completed.

Known compositions and thicknesses of the photoconductive layer can be used. In the case of forming a surface layer on the photoconductive layer, the above operation may be basically repeated. That is, the film forming gas and the etching gas may be supplied alternately.

More specifically, each of the outflow valves 2251 to 225
6 and the auxiliary valve 2260 are gradually opened, and the raw material gas necessary for the surface layer is supplied from the gas cylinders 2221-2226 through the gas introduction pipe 2114 to the reaction vessel 2.
Introduced into 110.

Next, each mass flow controller 211
According to 1-2216, each source gas is adjusted so as to have a desired flow rate. At this time, the inside of the reaction vessel 2110 is 1 To
The opening of the main valve 2118 is adjusted while watching the vacuum gauge 2119 so that the desired pressure is equal to or lower than rr. When the internal pressure is stabilized, the high-frequency power supply 2120 is set to a desired power, and high-frequency power is supplied to the cathode electrode 211 through the high-frequency matching box 2115 in a frequency range of 50 to 450 MHz to generate a high-frequency glow discharge. Each raw material introduced into the reaction vessel 2110 is decomposed by the discharge energy, and an a-BN deposition film is formed. After the desired film thickness is formed, the supply of the high-frequency power is stopped, the outflow valves 2251 to 2256 are closed to stop the flow of the source gases into the reaction vessel 2110, and the deposition of the deposited film is completed.

Next, the necessary one of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened, and the fluorine gas required for the etching process is supplied from the gas cylinders 2221 to 2226 through the gas introduction pipe 2114. Into the reaction vessel 2110. Next, the mass flow controllers 2111 to 2216 adjust the fluorine-based gas to a desired flow rate. At this time, the main valve 2118 is checked while watching the vacuum gauge 2119 so that the inside of the reaction vessel 2110 has a desired pressure of 1 Torr or less.
Adjust the opening of. When the internal pressure is stabilized, the high frequency power supply 2120 is set to a desired power at a frequency of 50 to 450.
MHz high frequency power to high frequency matching box 2115
To the cathode electrode 2111 to generate a high-frequency glow discharge.

This discharge energy causes the reaction vessel 21
The fluorine-based gas introduced into 10 is decomposed and reacts with the deposited film, whereby the deposited film is etched. After the etching of a desired film thickness is performed, the supply of the high-frequency power is stopped, and each outflow valve 2251 to 2256 is discharged.
Is closed, the flow of each source gas into the reaction vessel 2110 is stopped, and the etching of the surface of the deposited film is completed. The surface layer 304 is formed by repeating the film forming operation and the etching operation until a desired film thickness is obtained.

When switching between the film forming gas and the fluorine-based gas, the residual gas in the reaction vessel 2110 may be purged every time. However, from the viewpoint of film adhesion, the flow rate of the mass flow controller may be reduced without purging. It is preferable that the discharge is adjusted alternately and the discharge is continuously performed without stopping the discharge every time. During film formation, the cylindrical substrate 2112 may be rotated at a desired speed by a driving device (not shown).

As an example of a deposited film formed by this apparatus, there is an a-Si photosensitive member, and a typical cross-sectional view of a typical a-Si photosensitive member is shown in FIG. 3
It is shown in (B). FIG. 3A shows a single-layer photoreceptor in which the photoconductive layer 303 is a single layer in which the function is not separated, and FIG. 3B shows that the photoconductive layer 303 has the charge generation layer 305 and the charge transport layer 306. 2 is an example of a function-separated type photoconductor separated into two.

The a-Si light receiving member shown in FIG. 3A is composed of a conductive substrate 301 such as aluminum and a conductive substrate 3.
01 has a charge injection blocking layer 302, a photoconductive layer 303, and a surface layer 304 sequentially laminated. Here, the charge injection blocking layer 302 is formed from the conductive substrate 301 to the photoconductive layer 303.
And is provided as necessary. The photoconductive layer 303 is made of a non-single-crystal material containing at least silicon atoms, preferably an amorphous material, and shows photoconductivity. Further, the surface layer 3
Reference numeral 04 denotes a deposited film containing a boron atom, a nitrogen atom, a hydrogen atom, a halogen atom, or both atoms, and alternately repeating film formation and etching, and has a capability of retaining a latent image in an electrophotographic apparatus. is there. Hereinafter, the description will be made on the assumption that the charge injection blocking layer 302 is provided, except for the case where the effect differs depending on the presence or absence of the charge injection blocking layer 302. Also, the function of the charge injection blocking layer 302 is
3 may be taken.

In the a-Si type photoreceptor shown in FIG. 3B, the photoconductive layer 303 has a charge transport layer 306 made of a non-single-crystal material containing at least silicon atoms and carbon atoms, preferably an amorphous material. Charge generation layer 3 composed of a non-single-crystal material containing at least silicon atoms, preferably an amorphous material
Reference numeral 05 denotes a function-separated type having a configuration in which layers are sequentially stacked. When the photosensitive member is irradiated with light, mainly the charge generation layer 30
The carriers generated in 5 reach the conductive substrate 301 through the charge transport layer 306. Note that the arrangement order of the charge generation layer 305 and the charge transport layer 306 is opposite to that of FIG.
The charge generation layer 305 may be provided on the base 301 side.

FIG. 4 is a schematic view showing an example of an electrophotographic apparatus for explaining an example of an image forming process of the electrophotographic apparatus. The light receiving member 401 can be controlled in temperature by a sheet heater 423 provided inside. And rotate in the direction of the arrow X as necessary. Around the light receiving member 401, a main charger 402, an electrostatic latent image forming portion 403, a developing device 404, a transfer material supply system 405, a transfer charger 406.
(A), a separation charger 406 (b), a cleaner 450,
A transport system 408, a static elimination light source 409, and the like are provided as needed.

Hereinafter, an example of the image forming process will be described more specifically. The light receiving member 401 is uniformly charged by the main charger 402 to which a high voltage of +6 to 8 kV is applied. The light emitted from the lamp 410 is reflected on the document 412 placed on the platen glass 411 at the portion of the electrostatic latent image, passes through the mirrors 413, 414, 415, and forms an image by the lens 418 of the lens unit 417. Then, the light is guided through the mirror 416, projected as light carrying information, and an electrostatic latent image is formed on the light receiving member 401. Negative polarity toner is supplied from the developing device 404 to this latent image to form a toner image. Note that this exposure may be performed by scanning and exposing light carrying information using an LED array, a laser beam, a liquid crystal shutter, or the like without using reflection from the document 412.

On the other hand, a transfer material P such as paper is transferred to a transfer material supply system 40.
5, the leading end supply timing is adjusted by the registration roller 422, and the leading end is supplied toward the light receiving member 401. A positive electric field having a polarity opposite to that of the toner is applied to the transfer material P from the back surface in the gap between the transfer charger 406 (a) to which the high voltage of +7 to 8 kV is applied and the light receiving member 401, whereby the surface of the light receiving member is The negative polarity toner image is the transfer material P
Transfer to Then, 12-14 kVp-p, 300-
Separate charger 406 to which a high-voltage AC voltage of 600 Hz is applied
By (b), the light receiving member 401 is separated. Subsequently, the transfer material P passes through the transfer conveyance system 408 and passes through the fixing device 424.
And the toner image is fixed and carried out of the apparatus.

The toner remaining on the light receiving member 401 is collected by a cleaning roller 407 of a cleaner 450 and a cleaning blade 421 made of an elastic material such as silicone rubber or urethane rubber. Will be erased.

Reference numeral 420 denotes a blank exposing LED, which is a light receiving member as necessary so that unnecessary developer does not adhere to a non-image area such as a portion exceeding the width of the transfer material P of the light receiving member 401 and a blank portion. It is provided for exposing 401.

FIG. 5, FIG. 6 and FIG.
It is a schematic diagram for demonstrating an example of the apparatus (mass production type) of the light receiving member by VHF plasma CVD method of another form. FIG. 7 shows a schematic configuration diagram of the entire apparatus, and FIG.
Shows a schematic longitudinal sectional view of the reaction vessel section, and FIG. 6 shows a schematic transverse sectional view of the reaction vessel section.

In FIG. 5 to FIG. 7, reference numeral 5100 denotes a reaction vessel having a structure capable of maintaining a reduced pressure atmosphere. 51
An exhaust pipe 13 has one end opened into the reaction vessel 5111 and the other end communicating with an exhaust device (not shown). 513
Numeral 0 indicates a discharge space surrounded by the cylindrical film-forming substrate 5115. The high frequency power supply 5119 is electrically connected to the electrode 5118 via the high frequency matching box 5112. The cylindrical deposition substrate 5115 includes a holder 512.
It is installed on the rotating shaft 5114 in a state where it is set to 1. The raw material gas supply device 5200 includes SiH ₄ , H ₂ , CH ₄ ,
Cylinders 5221 to 5226 filled with source gases such as N ₂ , B ₂ H ₆ , and CF ₄ and etching gases, and valves 5231 to 5236, 5241 to 5246, and 52, respectively.
51-5256 and mass flow controller 521
1 to 5216, and a cylinder for each constituent gas is connected to a gas introduction pipe 51 in the reaction vessel 5100 via an auxiliary valve 5260.
17.

The high-frequency power supply used in the present invention has a frequency of at least 50 to 450 for forming the surface layer.
Anything that can output a frequency in the range of MHz can be used. Of course, it is desirable to output a frequency in a frequency range different from that at the time of forming the surface layer for the formation of another layer (or region), or to provide another power supply so as to output the frequency. Also. Any output can be used as long as it can generate power suitable for a device used in a range of 10 to 5000 W or more.

Further, the output fluctuation rate of the high frequency power supply is not particularly limited. As the matching box 5112 to be used, any configuration can be suitably used as long as it can match the load with the high frequency power supply 5119.
Further, as a method for achieving the matching, it is preferable that the adjustment is performed automatically. However, even if the adjustment is performed manually, the effect of the present invention is not affected at all.

The material of the electrode 5118 to which high-frequency power is applied is copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, or two or more of these materials. Composite materials and the like can be used. The shape is preferably a cylindrical shape, but an elliptical shape or a polygonal shape may be used if necessary.

The electrode 5118 may be provided with a cooling means if necessary. As specific cooling means, cooling by water, air, liquid nitrogen, a Peltier element, or the like is used as necessary.

The cylindrical film-forming substrate 5115 may have any material and shape according to the purpose of use. For example,
Regarding the shape, in the case of manufacturing an electrophotographic photoreceptor, a cylindrical shape is preferable, but a flat plate shape or another shape may be used as necessary. In the material, copper,
Aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and composite materials of two or more of these materials, as well as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, and poly Insulating materials such as vinyl chloride, polyvinylidene chloride, polystyrene, glass, quartz, ceramics and paper coated with a conductive material can be used.

[0070]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 A light receiving member was manufactured using the plasma CVD apparatus shown in FIG. The surface layer was formed by sequentially repeating the etching of the deposited film formed under the conditions shown in Table 1 and successively stacking. However, the thickness of the deposited film at this time was 1000 Å.

[0072]

[Table 1] The 1000 Å deposited film thus obtained was etched under the conditions shown in Table 2,
The etching of 500 angstroms was repeated to form a surface layer containing fluorine atoms with a total thickness of 3000 angstroms. Note that each gas of CF ₄ , CHF ₃ and ClF ₃ was used as a fluorine source,
Three light receiving members were prepared according to three types of fluorine sources.

[0073]

[Table 2] In order to evaluate the water repellency of the three light-receiving members, the contact angle of the surface was measured with pure water using a contact angle meter.
Higher water repellency than the membrane was obtained. Next, the three light-receiving members were mounted on a copying machine, and an accelerated durability test was performed in a high-temperature, high-humidity environment of 35 ° C. and a relative humidity of 90% to evaluate image deletion. However, each step of charging, exposure, development, transfer, separation, and scrape cleaning was sequentially repeated without using the heating means for the light receiving member.

(Accelerated Endurance Test) As the developer used for endurance, a developer containing an external additive such as strontium titanate for promoting polishing of the surface of the light receiving member is used. As the transfer material used for durability, A4 size recycled paper containing many components such as talc which has a high possibility of affecting image flow characteristics is used. Further, in order to promote the contamination of the charger wire, the paper is passed for 5 hours with a solid black image on the entire surface. Subsequently, the developing and cleaning steps are released, and non-paper passing durability of charging and exposure is performed for 5 hours. The above process is defined as one cycle, and a total of five cycles of accelerated durability are performed. Each time the cycle is completed, the evaluation of image deletion and the evaluation of image density unevenness are performed.

(Evaluation of Image Deletion) As an evaluation method of image deletion, evaluation was made using a test chart in which characters of 6 points or less were printed on the entire surface. Table 3 shows the results obtained by the above evaluation. The symbols in the table indicate the following determination results. “○” indicates a clear image without image deletion, “△” indicates a partial image deletion (no problem in practical use), and “×” indicates a full image flow , Respectively.

[0076]

[Table 3] As a result, no image defects such as image deletion and scratches occurred in any of the light receiving members even after the accelerated durability of 5 cycles. In addition, as a result of measuring the contact angle after 5 cycles of accelerated durability, the decrease in the contact angle was suppressed to 2% or less for any of the light receiving members as compared with the contact angle before the durability. That is, the retention rate is 98% or more, and the initial water repellency can be maintained even if any fluorine-based gas is used for the etching process. Furthermore, the charger wire stain after the cycle was evaluated by halftone density unevenness.

(Evaluation of Image Density Unevenness) Hereinafter, a method of evaluating image density unevenness will be described with reference to FIG. The main charger 4 is controlled so that the dark area potential at the position of the developing device 404 becomes 400 V.
02, the document 412 having a reflection density of 0.3 is placed on the document table 411, and the lighting voltage of the halogen lamp 410 is adjusted so that the bright portion potential becomes 200 V.
A halftone image of the plate was created. The image is used to observe streak-like density unevenness caused by wire contamination.

Table 4 shows the results obtained by the above evaluation.
The symbols in the table indicate the following determination results. "○"
Indicates a clear image without density unevenness, “△” indicates partial density unevenness (no problem in practical use), and “x” indicates that streak-shaped density unevenness may occur on the entire surface of the image. Shown respectively.

[0079]

[Table 4] No streak-like density unevenness caused by wire contamination occurs in any of the light receiving members even after accelerated durability of 5 cycles. From this result, the initial cleaning property can be maintained if the gas used for the etching treatment is a fluorine-based gas.

Comparative Example 1 Using the plasma CVD apparatus shown in FIG. 2, a light receiving member was manufactured under the conditions shown in Table 1. When forming the surface layer, a deposited film having a thickness of 3500 angstroms is formed at a time, and the thus obtained deposited film is subjected to a 500 angstrom etching by fluorine treatment only on the outermost surface under the conditions shown in Table 2. The thickness of the surface layer was set to 3000 Å.

The fluorine source is CF ₄ , CHF ₃ , C
_Three light-receiving members were prepared using each gas of 1F ₃ according to three kinds of fluorine sources. In order to evaluate the water repellency of the three light receiving members, the contact angle of the surface was measured with pure water in the same manner as in Example 1. As a result, the a-BN film containing no fluorine atom was found for any of the light receiving members. Higher water repellency was obtained.

Next, these three light receiving members were used in Example 1.
In the same manner as in the above, an accelerated durability test was performed in a high-temperature, high-humidity environment at 35 ° C. and a relative humidity of 90%, and image deletion was evaluated. However, each step of charging, exposure, development, transfer, separation, and scrape cleaning was sequentially repeated without using the heating means of the light receiving member as in Example 1.

Table 3 shows the results obtained by the above evaluation.
As a result, in any of the light receiving members, image deletion may occur after three cycles of durability. As a result of measuring the contact angle of the light receiving member after 5 cycles of durability, the value of the contact angle of any light receiving member before the endurance was 50%.
% Or less. Further, the contamination of the charger wire after each cycle was evaluated in the same manner as in Example 1 by the halftone density unevenness.

Table 4 shows the results obtained by the above evaluations.
As a result, streak-like density unevenness caused by wire contamination occurred after three cycles of durability in any of the light receiving members.

Example 2 By the same method as in Example 1, film formation and etching were repeated to a total thickness of 3000 Å to form a surface layer. However, in forming the surface layer, the thickness of the deposited film by the film formation and the thickness of the etched film by the fluorine treatment were set to the five types shown in Table 5 below. Note that CF ₄ gas was used as a fluorine source.

[0086]

[Table 5] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 to evaluate the water repellency of the five light-receiving members A to E, any of the light-receiving members did not contain a fluorine atom. -Higher water repellency than the BN film.

Next, these five light receiving members were used in Example 1.
In the same manner as in the above, an accelerated durability test was performed in a high-temperature, high-humidity environment at 35 ° C. and a relative humidity of 90% to evaluate image deletion. However, similar to the first embodiment, the charging is performed without using the heating means of the light receiving member.
Each step of exposure, development, transfer, separation, and scrape cleaning was sequentially repeated.

Table 6 shows the results obtained by the above evaluation.
As a result, no image defects such as image deletion and scratches occurred in any of the light receiving members even after the accelerated durability of 5 cycles. In addition, as a result of measuring the contact angle after 5 cycles of accelerated endurance, the decrease in the contact angle was suppressed to 2% or less as compared to the contact angle before endurance for any of the light receiving members, and one etching film was used. It has been found that if the thickness is 20 Å or more, the initial water repellency can be maintained.

[0089]

[Table 6] Further, the contamination of the charger wire after each cycle was evaluated in the same manner as in Example 1 by the halftone density unevenness. Table 7 shows the results obtained by the above evaluation. No streak-like density unevenness caused by wire contamination occurred in any of the light receiving members even after 5 cycles of durability. From this result, it can be seen that the initial cleaning property is maintained if the thickness of one etching is 20 angstroms or more. It turned out that it was done.

[0090]

[Table 7] Comparative Example 2 A light receiving member was formed under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG. However,
At this time, the surface layer was continuously formed without being etched in the middle, and had a film thickness of 3000 Å.

This light receiving member was formed by a method similar to that of the first embodiment.
An accelerated durability test was performed in a high-temperature, high-humidity environment of 90 ° C. and a relative humidity of 90%, and image deletion was evaluated. However, each step of charging, exposure, development, transfer, separation, and scrape cleaning was sequentially repeated without using the heating means of the light receiving member as in Example 1. Table 6 shows the results obtained by the above evaluation.

As a result, image deletion occurred even after one cycle of durability. As a result of measuring the contact angle of the light receiving member after the above 5 cycles of durability, the contact angle was reduced to 50% or less from the value of the contact angle before the durability, and the initial contact angle of the surface layer containing no fluorine atom could be maintained. Not confirmed.

In addition, the contamination of the charger wire after each cycle was evaluated in the same manner as in Example 1 by halftone density unevenness. Table 7 shows the results obtained by the above evaluation. As a result, streak-like density unevenness caused by wire contamination may occur after two cycles of durability.

Example 3 In the same manner as in Example 1, the surface layer was repeatedly formed and etched a plurality of times to a total thickness of 4000 Å to form a surface layer. However, the deposited film thickness of the surface layer and the etching film thickness by the fluorine treatment were performed in six ways shown in Table 8. Note that CF ₄ gas was used as a fluorine source.

[0095]

[Table 8] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 to evaluate the water repellency of the six light-receiving members F to K, any of the light-receiving members contained no fluorine atom. Higher water repellency was obtained than with the -BN film.

Next, these six light receiving members were used in Example 1.
In the same manner as in the above, an accelerated durability test was performed in a high-temperature, high-humidity environment at 35 ° C. and a relative humidity of 90% to evaluate image deletion. However, similar to the first embodiment, the charging is performed without using the heating means of the light receiving member.
Each step of exposure, development, transfer, separation, and scrape cleaning was sequentially repeated.

Table 11 shows the results obtained by the above evaluation. As a result, no image deletion occurred even after 5 cycles of durability except for the light receiving member K. In addition, as a result of measuring the contact angle after 5 cycles of durability, the contact angles other than the light receiving member K were suppressed to a decrease of 2% or less as compared with the contact angles before durability, and the initial water repellency was maintained. . Regarding the light receiving member K, the contact angle after 4 cycles of durability was 1 value lower than the value before durability.
It decreased by 0% and decreased by 20% after 5 cycles of durability. No image defects such as scratches occurred on any of the light receiving members.

Further, the contamination of the charger wire after each cycle was evaluated by the halftone density unevenness in the same manner as in Example 1. Table 12 shows the results obtained in this evaluation. As a result, no streak-like density unevenness caused by wire contamination did not occur in any of the light receiving members even after 5 cycles of durability.

From the above results, the film thickness per layer of the surface layer to be laminated by the film forming and etching operations is 2
500 angstroms or less has been found to be preferred. If the thickness is less than 30 angstroms, the uniformity of the formed film may not be sufficient, and the number of times of film formation and etching increases, so that the total surface layer formation time becomes longer.

Example 4 A surface layer was formed by repeating the film forming and etching processes to a total thickness of 4000 Å in the same manner as in Example 1. However, the surface layer was prepared under the conditions shown in Table 9 using a 13.56 MHz high frequency power supply.

[0101]

[Table 9] In addition, the deposition thickness of the surface layer and the etching thickness by the fluorine treatment were performed in six ways shown in Table 10 below. The fluorine source was prepared using CF ₄ gas.

[0102]

[Table 10] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 in order to evaluate the water repellency of the six light receiving members F ′ to K ′, any of the light receiving members contained a fluorine atom. Higher water repellency was obtained than the non-a-BN film.

Next, these six light receiving members were used in Example 1.
Similarly to the above, an accelerated durability test of 5 cycles was performed in a high-temperature, high-humidity environment of 35 ° C. and a relative humidity of 90% to evaluate image deletion.
However, each step of charging, exposure, development, transfer, separation, and scrape cleaning was sequentially repeated without using the heating means of the light receiving member as in Example 1.

Table 11 shows the results obtained by the above evaluation. As a result, no image deletion occurred even after the endurance of 5 cycles except for the light receiving member K ′. In addition, as a result of measuring the contact angle after 5 cycles of durability, any of the light receiving members was suppressed to 30% or less of the value of the contact angle before the durability, and the water repellency that can withstand practical use was maintained. . No image defects such as scratches occurred on any of the light receiving members.

[0105]

[Table 11] Further, the contamination of the charger wire after each cycle was evaluated in the same manner as in Example 1 by the halftone density unevenness. Table 12 shows the results obtained by the above evaluation. As a result, it was found that, in any of the light receiving members, even after 5 cycles of durability, streak-like density unevenness caused by wire contamination was at a level that was not problematic in practical use. However, all of the light receiving members of Example 4 were partially uneven in density after 5 cycles of durability.

[0106]

[Table 12] From the above results, by using the frequency of the high-frequency power supply used for forming the surface layer at 50 to 450 MHz, the structure of the film is further densified, the fluorine atom content efficiency is improved, and the conventional 13.56 MHz frequency is improved. The cleaning property is further improved as compared with the case where a high frequency power supply is used.

Example 5 A light receiving member was manufactured under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG. However, the thickness of one deposition film formed on the surface layer was 1000 Å. An operation of subjecting the deposited film thus obtained to a fluorine treatment under the conditions shown in Table 2 and performing etching at 500 Å was repeated to form a surface layer containing fluorine atoms having a film thickness shown in Table 13. The fluorine source was prepared using CF ₄ gas under the following four conditions.

[0108]

[Table 13] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 to evaluate the water repellency of the four light receiving members L to O, fluorine atoms were found to be present in any of the light receiving members. Water repellency higher than that of the a-BN film not containing was obtained.

Next, the four light receiving members were used in Example 1.
In the same manner as in the above, an accelerated durability test was performed in a high-temperature, high-humidity environment at 35 ° C. and a relative humidity of 90% to evaluate image deletion. However, similar to the first embodiment, the charging is performed without using the heating means of the light receiving member.
Each step of exposure, development, transfer, separation, and scrape cleaning was sequentially repeated.

Table 14 shows the results obtained in the above evaluation. No image defects such as image deletion and scratches occurred in any of the light receiving members even after 5 cycles of durability. Further, as a result of measuring the contact angle after 5 cycles of durability, the contact angle of any of the light receiving members was suppressed to 2% or less as compared with the contact angle before the durability, and the initial water repellency was maintained. . From this result, it was found that the effects of the present invention can be obtained by repeating the operations of the film formation and the etching treatment twice or more.

[0111]

[Table 14] Further, the charger wire stain after each cycle was evaluated by halftone density unevenness in the same manner as in Example 1. Table 15 shows the results obtained in this evaluation. As a result, no streak-like density unevenness caused by wire contamination did not occur in any of the light receiving members even after 5 cycles of durability.

[0112]

[Table 15] [Embodiment 6] Using the plasma CVD apparatus shown in FIG.
Under the conditions shown in Table 16, a light receiving member was manufactured. However, the thickness of each deposited film formed in the formation of the surface layer was 1000 Å. The thus obtained deposited film was repeatedly subjected to a 500 angstrom etching process by fluorine treatment under the conditions shown in Table 2 to form a surface layer containing fluorine atoms having a total thickness of 3000 angstrom.

[0113]

[Table 16] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 in order to evaluate the water repellency of the light receiving member, the a-BN film containing no fluorine atom for any of the light receiving members, High water repellency was obtained.

Next, this light-receiving member was subjected to an accelerated durability test in a high-temperature and high-humidity environment of 35 ° C. and a relative humidity of 90% in the same manner as in Example 1 to evaluate image deletion. However, similar to the first embodiment, charging, exposure,
Each step of development, transfer, separation, and scrape cleaning was sequentially repeated.

Table 17 shows the results obtained by the above evaluation. As a result, no image defects such as image deletion and scratches were generated even after 5 cycles of durability. Further, as a result of measuring the contact angle after 5 cycles of durability, the contact angle was reduced to 2% or less as compared with the contact angle before durability, and the initial water repellency was maintained.

[0116]

[Table 17] Further, the charger wire stain after each cycle was evaluated by halftone density unevenness in the same manner as in Example 1. Table 18 shows the results obtained in this evaluation. As a result, no streak-like density unevenness caused by wire contamination did not occur even after 5 cycles of durability. From the above results, it was found that the layer structure other than the surface layer and the discharge frequency were not affected.

[0117]

[Table 18] [Embodiment 7] The plasma CV described with reference to FIGS.
Using the D apparatus, a light receiving member was manufactured under the conditions shown in Table 1. However, at this time, the thickness of the deposited film by one film formation was set to 1000 Å, and
The operation of etching at 500 angstroms by applying a fluorine treatment under the conditions shown in the following was repeated to form a surface layer containing fluorine atoms having a total thickness of 3000 angstroms.

When the contact angle of the surface was measured with pure water in the same manner as in Example 1 in order to evaluate the water repellency of the light receiving member, the a-BN film containing no fluorine atom was found for any of the light receiving members. Higher water repellency was obtained.

Next, this light-receiving member was subjected to an accelerated durability test in a high-temperature, high-humidity environment of 35 ° C. and a relative humidity of 90% in the same manner as in Example 1 to evaluate image deletion. In this case, similarly to Example 1, the steps of charging, exposure, development, transfer, separation, and scrape cleaning were sequentially repeated without using the heating means for the light receiving member.

Table 19 shows the results obtained in the above evaluation. As a result, image defects such as image deletion and scratches did not occur at all even after 5 cycles of durability. Further, as a result of measuring the contact angle after 5 cycles of durability, the contact angle was reduced to 2% or less as compared with the contact angle before the durability, and the initial water repellency was maintained.

[0121]

[Table 19] Further, the charger wire stain after each cycle was evaluated by halftone density unevenness in the same manner as in Example 1. Table 20 shows the results obtained in this evaluation. As a result, no streak-like density unevenness caused by wire contamination did not occur even after 5 cycles of durability. From the above results, it has been found that good effects can be obtained according to the manufacturing method of the present invention regardless of the configuration of the film forming apparatus.

[0122]

[Table 20] Example 8 A light receiving member was manufactured under the conditions shown in Table 21 using the plasma CVD apparatus shown in FIG. However, the thickness of each deposited film formed in the formation of the surface layer was 1000 Å. The thus-obtained deposited film was repeatedly subjected to a 500 angstrom etching process by fluorine treatment under the conditions shown in Table 2 to form a surface layer containing fluorine atoms having a total thickness of 3000 angstrom.

[0123]

[Table 21] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 to evaluate the water repellency of the light receiving member, any of the light receiving members was higher than the a-BN film containing no fluorine atom. Water repellency was obtained.

Next, the light receiving member was subjected to accelerated durability in a high temperature and high humidity environment of 35 ° C. and a relative humidity of 90% in the same manner as in Example 1, and the image deletion was evaluated. However, each step of charging, exposure, development, transfer, separation, and scrape cleaning was sequentially repeated without using the heating means of the light receiving member as in Example 1.

Table 22 shows the results obtained by the above evaluation. As a result, image defects such as image deletion and scratches did not occur at all even after 5 cycles of durability. Further, as a result of measuring the contact angle after 5 cycles of durability, the contact angle was reduced to 2% or less as compared with the contact angle before the durability, and the initial water repellency was maintained.

[0126]

[Table 22] Further, the charger wire stain after each cycle was evaluated by halftone density unevenness in the same manner as in Example 1. Table 23 shows the results obtained in this evaluation. As a result, no streak-like density unevenness caused by wire contamination did not occur even after 5 cycles of durability. From the above results, the effects of the present invention were sufficiently obtained even when a fluorine-based gas was used as the film forming gas for the surface layer.

[0127]

[Table 23] Example 9 Using the plasma CVD apparatus shown in FIG. 2, a light receiving member was manufactured under the conditions shown in Table 24. However, in forming the surface layer, the frequency of the high-frequency power is set to 13.
The frequency is set to 56 MHz, and the thickness of each deposited film is 100
0 angstrom. The deposited film obtained in this manner was subjected to a fluorine treatment under the conditions shown in Table 24 by 50 treatment.
The etching operation of 0 Å was repeated to form a surface layer containing fluorine atoms with a total thickness of 3000 Å.

[0128]

[Table 24] When the contact angle of the surface was measured with pure water in the same manner as in Example 1 to evaluate the water repellency of the light receiving member, any of the light receiving members was higher than the a-BN film containing no fluorine atom. Water repellency was obtained. Next, the light-receiving member was subjected to an accelerated durability test in a high-temperature, high-humidity environment of 35 ° C. and 90% relative humidity in the same manner as in Example 1 to evaluate image deletion. However, each step of charging, exposure, development, transfer, separation, and scrape cleaning was sequentially repeated without using the heating means of the light receiving member as in Example 1.

Table 25 shows the results obtained in the above evaluation. As a result, image defects such as image deletion and scratches did not occur at all even after 5 cycles of durability. Further, as a result of measuring the contact angle after 5 cycles of durability, the contact angle was reduced to 2% or less as compared with the contact angle before the durability, and the initial water repellency was maintained.

[0130]

[Table 25] Further, the charger wire stain after each cycle was evaluated by halftone density unevenness in the same manner as in Example 1. Table 26 shows the results obtained in this evaluation. As a result, even after 5 cycles of durability, streak-like density unevenness caused by wire contamination did not occur. However, for forming the surface layer,
In some cases, it takes five times as long, and in some cases, practically no problematic scratches occur on the image after 5 cycles of durability.

[0131]

[Table 26] From the above results, the effect of the present invention can be sufficiently obtained even when the discharge frequency used for film formation and etching of the surface layer is set to 13.56 MHz and a fluorine-based gas is used as the film formation gas for the surface layer. In consideration of the deposition rate and mechanical strength, it is desirable to use a discharge frequency of 50 to 450 MHz for forming and etching the surface layer.

[0132]

As described above in detail, in the present invention, the light receiving member is formed by repeating the film formation using the high frequency power of 50 to 450 MHz and the etching treatment with the fluorine-based gas a plurality of times. The entire region contains fluorine atoms effectively. When this is used for an electrophotographic apparatus or the like, it becomes possible to sufficiently prevent the corona discharge product from adhering even if the steps of charging, exposure, development, transfer, separation and cleaning are repeated.

Further, as a result of repeating the scrape cleaning with a blade for a long time without impairing the hardness of the surface protective layer, even if the outermost surface of the light receiving member is polished, the water repellency of the surface layer can be maintained, and There is substantially no change in water adsorption due to the difference between the two, and it is possible to prevent the occurrence of image deletion and image blurring without providing a heating means for the light receiving member.

Further, the cleaning property is excellent, the cleaning property can be maintained even when the copying process is repeated, and the image density unevenness caused by the contamination of the charger wire due to the scattering of the toner can be prevented. Became. In addition, since there is no need to heat the light receiving member, the types of toner that can be used can be significantly increased.

It is needless to say that modifications and combinations can be made as appropriate within the scope of the gist of the present invention, and the present invention is not limited to the above embodiments.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a preferred example of a configuration of a surface layer of a light receiving member of the present invention.

FIG. 2 is a schematic configuration diagram showing an example of a deposition apparatus used for manufacturing a light receiving member by a VHF-PCVD method applicable to the present invention.

FIG. 3 is a schematic sectional view showing a configuration example of a light receiving member of the present invention.

FIG. 4 is a schematic cross-sectional view illustrating an example of an electrophotographic apparatus.

FIG. 5 is a schematic longitudinal sectional view showing an example of a deposition apparatus used when manufacturing a light receiving member by a VHF-PCVD method applicable to the present invention.

FIG. 6 is a schematic cross-sectional view of the deposition apparatus of FIG.

FIG. 7 is a schematic configuration diagram illustrating the overall configuration of the deposition apparatus of FIG. 5;

[Explanation of symbols]

101 Area where fluorine atoms are diffused 102 Area where fluorine atoms are present in a bonded state 2100, 5100 Deposition apparatus 2110, 5111 Reaction vessel 2111, 5118 Cathode electrode 2112, 5115 Conductive substrate 2113, 5116 Heater for substrate heating 2114, 5117 Gas inlet pipe 2115, 5112 High frequency matching box 2116 Gas pipe 2117 Leak valve 2118 Main valve 2119 Vacuum system 2120, 5119 High frequency power supply 2121 Insulating material 2122 Insulating shield plate 2123 Receiver 2200, 5200 Gas supply device 2211-2216, 5211-5216 Mass flow Controllers 2221 to 2226, 5221 to 5226 Cylinders 2231 to 2236, 5231 to 5236 Valves 2241 to 2246 5241 to 5246 Inflow valves 2251 to 2256, 5251 to 5256 Outflow valves 2260, 5260 Auxiliary valves 2261 to 2266, 5261 to 5266 Pressure regulator 301 Conductive substrate 302 Charge injection blocking layer 303 Photoconductive layer 304 Surface layer 305 Charge generation layer 306 Charge transport layer 401 Light receiving member 402 Main charger 403 Electrostatic latent image forming portion 404 Developing device 405 Transfer paper supply system 406 (a) Transfer charger 406 (b) Separator charger 407 Cleaning roller 408 Transport system 409 Static elimination light source 410 Halogen lamp 411 Document table 412 Document 413 to 416 Mirror 417 Lens unit 418 Lens 419 Paper feed guide 420 Blank exposure LED 421 Cleaning blade 422 Registration roller 423 Surface heater 424 Fixer 450 Cleaner 5120 Motor 5121 Holder

Claims (30)

[Claims] 1. A method for forming a surface layer by alternately repeating film formation and etching of a layer of a non-single-crystal material containing boron atoms and nitrogen atoms a plurality of times in a reaction vessel capable of reducing pressure. A method for producing a light receiving member. 2. The method according to claim 1, wherein the gas used for the etching is a gas containing fluorine. 3. The method according to claim 2, wherein the gas containing fluorine is CF ₄ , C
_{3. The} method for manufacturing a light receiving member according to claim 2, wherein the method includes at least one of HF ₃ , C ₂ F ₆ , and ClF ₃ . 4. The method according to claim 1, wherein the film thickness etched by one etching is 20 Å or more.
A method for producing the light receiving member according to the above. 5. The film thickness etched by one etching is 50 Å or more.
A method for producing the light receiving member according to the above. 6. A film thickness deposited in one time of the film formation is 3
The method for producing a light receiving member according to claim 1, wherein the light receiving member has a thickness of 0 to 2500 angstroms. 7. A film thickness deposited in one time of the film formation is 6
The method for producing a light receiving member according to claim 1, wherein the thickness is 0 to 1000 Å. 8. The method according to claim 1, wherein the thickness of the surface layer formed by one set of the film formation and the etching is 10 to 2,000 angstroms. 9. The method according to claim 1, wherein the thickness of the surface layer formed by one set of the film formation and the etching is 40 to 1000 angstroms. 10. The method for manufacturing a light receiving member according to claim 1, wherein a region where fluorine is bonded is formed by said film formation and etching. 11. The method according to claim 10, wherein the thickness of the region is 1 to 500 angstroms. 12. The method according to claim 1, wherein the surface layer is formed on a receiving layer formed on the substrate. 13. The method according to claim 12, wherein the receiving layer has photoconductivity. 14. The method according to claim 12, wherein the receiving layer has a photoconductive layer. 15. The method according to claim 14, wherein the photoconductive layer is of a single-layer type. 16. The method according to claim 14, wherein the photoconductive layer is of a function-separated type. 17. The method according to claim 14, wherein the photoconductive layer has a charge transport layer and a charge generation layer. 18. The method according to claim 12, wherein the receiving layer has a charge injection blocking layer on the substrate side. 19. The method according to claim 12, wherein the receiving layer comprises a non-single-crystal material having silicon atoms as a base. 20. The method according to claim 1, wherein the surface layer further contains a fluorine atom. 21. The method according to claim 1, wherein the non-single-crystal material layer includes an amorphous material. 22. The method according to claim 1, wherein the high-frequency power used for forming the surface layer is 50 to 450 MHz. 23. The method according to claim 1, wherein the high-frequency power used for etching the surface layer is 50 to 450 MHz. 24. The method according to claim 1, wherein the high-frequency power used for forming and etching the surface layer is 50 to 450 MHz. 25. The method according to claim 12, wherein the high-frequency power used for forming the receiving layer is 1 to 450 MHz. 26. A light receiving member produced by the method for manufacturing a light receiving member according to claim 1. 27. An electrophotographic apparatus having a light receiving member made by the method for manufacturing a light receiving member according to claim 1. 28. An electrophotographic process in which the steps of charging, exposing, developing, transferring and cleaning are sequentially performed using the light receiving member produced by the method of manufacturing a light receiving member according to claim 1. 29. The electrophotographic process according to claim 28, wherein the light receiving member is performed without being heated by a heating means. 30. A layer of a non-single-crystal material containing boron atoms and nitrogen atoms is formed on a receiving layer formed on a substrate in a reaction vessel capable of reducing pressure by film formation and etching. Charging the light receiving member in sequence without heating the light receiving member on the surface layer; irradiating the charged light receiving member with light to form an electrostatic latent image; Developing a surface of the member to form a toner image, transferring the formed toner image onto a recording material, and cleaning the surface of the light receiving member after transferring the toner image. An electrophotographic process.